EP3325526B1 - A coating additive - Google Patents

A coating additive Download PDF

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Publication number
EP3325526B1
EP3325526B1 EP15898528.3A EP15898528A EP3325526B1 EP 3325526 B1 EP3325526 B1 EP 3325526B1 EP 15898528 A EP15898528 A EP 15898528A EP 3325526 B1 EP3325526 B1 EP 3325526B1
Authority
EP
European Patent Office
Prior art keywords
ethylenically unsaturated
dry weight
coating
meth
acetoacetoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP15898528.3A
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German (de)
English (en)
French (fr)
Other versions
EP3325526A1 (en
EP3325526A4 (en
Inventor
Liqiang Fan
Rui Wang
Jianming Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Rohm and Haas Co
Original Assignee
Dow Global Technologies LLC
Rohm and Haas Co
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Publication date
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Publication of EP3325526A1 publication Critical patent/EP3325526A1/en
Publication of EP3325526A4 publication Critical patent/EP3325526A4/en
Application granted granted Critical
Publication of EP3325526B1 publication Critical patent/EP3325526B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention provides a coating additive, and a coating formulation comprising the coating additive.
  • EP2412423A1 discloses filter elements constructed of a filter support material coated with an acetoacetate-functional polymeric composition that reacts with and removes aldehydes, especially formaldehyde, present in gases such as air.
  • WO9927025A1 discloses a coating composition comprising a polymeric additive.
  • US2012157609A1 discloses substituted 3-oxopentanoates. Also disclosed are emulsion polymers, suspension polymers, and solution polymers that comprise residues from the substituted 3-oxopentanoate monomers, and that may also include one or more additional ethylenically unsaturated monomers.
  • Acetoacetoxy or acetoacetamide functional monomers such as acetoacetoxyethyl methacrylate (AAEM) is commonly used to make self-crosslinking, room-temperature-cure emulsion copolymers that may be used to produce coatings having good hardness and chemical and block resistance.
  • AAEM acetoacetoxyethyl methacrylate
  • the acetoacetoxy-functionality of the AAEM monomer can cross-link via an "oxidative cure" or react with an added cross-linker such as a diamine to produce a cured film. Due to the similar chemistry, the acetoacetoxy functionality can also be employed to react with formaldehyde.
  • AAEM AAEM was usually polymerized in coating binders to achieve its above roles. This limited AAEM's use.
  • acetoacetoxy functionality has a much higher effectiveness when it is added through coating additives rather than through coating binders.
  • the present invention provides a coating additive (co)polymer comprising, as copolymerized units, by dry weight based on total dry weight of the copolymer,
  • the present invention further provides a coating formulation comprising higher than 0.04% by dry weight based on total dry weight of the coating formulation, the acetoacetoxy or acetoacetamide functional ethylenically unsaturated monomer.
  • the coating additive of the present invention is a (co)polymer comprising, as copolymerized units, by dry weight based on total dry weight of the copolymer,
  • Acetoacetoxy or acetoacetamide functional ethylenically unsaturated monomers are monomers having at least one ethylenic unsaturation functional group and at least one acetoacetyl moiety attached to the ethylenic unsaturation functional group, and having the following structure:
  • acetoacetoxy or acetoacetamide functional ethylenically unsaturated monomers include acetoacetoxyalkyl (meth)acrylate such as acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, and 2,3-di(acetoacetoxy) propyl (meth)acrylate; allyl acetoacetate; vinyl acetoacetate; and acetoacetamide having the following structure: wherein R 6 is selected from H and methyl.
  • the acetoacetoxy or acetoacetamide functional ethylenically unsaturated monomers are selected from acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, allyl acetoacetate, 2,3-di(acetoacetoxy) propyl (meth)acrylate, and any combinations thereof.
  • the water soluble ethylenically unsaturated monomers are monomers having the following structure: D-(CH 2 CH 2O ) h -(CH 2 CH(CH 3 )O) k -E;
  • Suitable examples of the water soluble ethylenically unsaturated monomer include methoxy polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, hydroxypropyl (meth)acrylate, vinylsulfonic acid sodium (SVS), sodium p-styrenesulfonate (SSS), acrylamide (AM), and N-hydroxymethyl (meth)acrylamide.
  • Commercially available products include HOMASYTER TM MPEG-MA commercially available from Zhejiang Huangma chemical industry group Co., Ltd., and VTSIOMER TM MPEG 1005 MA W, VTSIOMER TM MPEG 2005 MA W, VTSIOMER TM MPEG 5005 MA W commercially available from Evonik Industries AG.
  • the water soluble ethylenically unsaturated monomers are selected from methoxypolyethylene glycol methacrylate, polyethylene glycol (meth)acrylate, and the combination thereof.
  • the emulsion or solution polymerization techniques used to prepare the (co)polymer are well known in the art.
  • Conventional surfactants may be used as anionic and/or nonionic emulsifiers such as alkali metal or ammonium alkyl sulfates, alkyl sulfonic acids, fatty acids, and oxyethylated alkyl phenols.
  • the amount of surfactant used is usually 0.1% to 6% by dry weight, based on the dry weight of total monomers. Either thermal or redox initiation processes may be used.
  • free radical initiators may be used and suitable examples include hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, ammonium, and alkali persulfates, in which the alkali include sodium and potassium, typically at a level of 0.01% to 3.0% by dry weight, based on the dry weight of total monomers.
  • Redox systems using the same initiators coupled with a suitable reductant such as sodium hydrosulfite, isoascorbic acid, and sodium bisulfite may be used at similar levels, optionally in combination with metal ions such as iron and copper, optionally further including complexing agents for the metal.
  • Chain transfer agents such as mercaptans may be used to adjust the molecular weight of the (co)polymers.
  • the monomer mixture may be added neat or as an emulsion in water.
  • the monomer mixture may be added in a single addition or in multiple additions or continuously over the reaction period using a uniform or varying composition.
  • Additional ingredients such as free radical initiators, oxidants, reducing agents, chain transfer agents, neutralizers, surfactants, and dispersants may be added prior to, during, or subsequent to any of the stages.
  • the acetoacetoxy or acetoacetamide functional ethylenically unsaturated monomer may be added to the coating additive at a dry weight percentage of higher than 0.04%, preferably from 0.1% to 2%, and more preferably from 0.2% to 1.5%, based on total dry weight of the coating formulation.
  • the coating formulation was drawn down on a black vinyl panel using a 200nm film caster, and was air dried in the horizontal position for one day.
  • the coating formulation was further drawn down on the back side of the panel using the 200nm film caster, and was air dried in the horizontal position for 7 days. 5cm ⁇ 1cm coating film samples were cut for the test.
  • the coating film samples were fixed with clips and put into well-sealed test bottles.
  • Formaldehyde was injected into the test bottle via small hole through the bottle sap.
  • a 3-methyl-2-benzothiazolinone hydrazone (MBTH) solution was injected into the test bottle to absorb formaldehyde residue.
  • the formaldehyde content in the absorption solution was tested via spectrophotometer method. The less formaldehyde content remained in the solution, the higher formaldehyde abatement effectiveness of the coating film.
  • the formaldehyde abatement effectiveness was expressed in percentage. The higher the percentage was, the higher the formaldehyde abatement effectiveness.
  • a monomer mixture was prepared by mixing 370g deionized water (DI), 80g (99.0% active) acetoacetoxyethyl (meth)acrylate, and 162.8g HOMASYTER TM MPEG-MA polyethylene glycol modified methacrylate.
  • the temperature was lowered to 66°C, and 1.06g sodium persulfate in 10g DI water was added and held for 15min. Then the temperature was further cooled to 40°C, and then 15g hydrogen peroxide (35% active) in 10g DI water was added into the flask and held for 5min. The flask was cooled down to room temperature and then 22g ethanolamine (50% active) was added with efficient stirring.
  • the prepared product is a (co)polymer dispersion of Coating Additive 1 having a 10.1% solid and a pH value of 3.54.
  • the (co)polymer dispersion of Coating Additive 2 was prepared according to the above procedure with only the monomer mixture changed to 370g deionized water (DI), 40g (99.0% active) acetoacetoxyethyl (meth)acrylate, and 217.5g HOMASYTER TM MPEG-MA polyethylene glycol modified methacrylate.
  • the prepared (co)polymer dispersion of Coating Additive 2 had a 9.58% solid and a pH value of 3.89.
  • Binder 1 was prepared from a monomer mixture that contained 501.7g DI water, 23.94g sodium dodecyl benzene sulfonate (DS-4, 22.5% active), 747g butyl acrylate, 652.9g methyl methacrylate, 22.41g methacrylic acid, and 74.7g acetoacetoxyethyl methacrylate. 47.2g of the monomer mixture was added to a kettle containing a mixture of 1317.9g DI water and 10.64g DS-4 (22.5% active) and was heated to 85°C. 2.26g sodium persulfate (SPS) dissolved in 50g DI water was then added as an initiator.
  • SPS sodium persulfate
  • Binder 2 was prepared according to the above procedure with only the monomer mixture changed to 501.7g DI water, 23.94g sodium dodecyl benzene sulfonate (DS-4, 22.5% active), 747g butyl acrylate, 725.2g methyl methacrylate, 22.41g methacrylic acid, and 2.39g acetoacetoxyethyl methacrylate.
  • Binder 3 was prepared according to the above procedure with only the monomer mixture changed to 501.7g DI water, 23.94g sodium dodecyl benzene sulfonate (DS-4, 22.5% active), 747g butyl acrylate, 727.6g methyl methacrylate, and 22.41g methacrylic acid.
  • Coating formulations 1 to 10 were prepared according to the procedure of Table 1 with detailed differences shown in Table 2. TABLE 1.
  • Binder 1 contained 5% AAEM, while Binder 3 contained no AAEM.
  • Inventive Coatings 2 to 5 comprised Binder 3 and therefore comprised no AAEM in the binder compositions, but they comprised different AAEM loadings in the additives.
  • Comparative Coating 1 comprised Binder 1 and therefore comprised AAEM in the binder composition, but it did not comprise any AAEM in the additive.
  • the total AAEM loadings in the Inventive Coatings 2 to 5 were much lower than that in Comparative Coating 1. To achieve similar formaldehyde abatement effectiveness, AAEM loadings in the Coatings could be significantly less if AAEM was added in the additive rather than in the binder composition.
  • Comparative Coating 1 had the similar formaldehyde abatement effectiveness as Inventive Coating 4, and the AAEM loading in Comparative Coating 1 was 1.38%, while the AAEM loading in Inventive Coating 4 was only 0.17% by dry weight based on total dry weight of the coating composition.
  • Binder 2 contained 0.16% AAEM.
  • Inventive Coating 8 and Comparative Coating 9 comprised Binder 3 and therefore comprised no AAEM in the binder compositions, but they comprised different AAEM loadings in the additives.
  • Comparative Coating 7 comprised Binder 2 and therefore comprised AAEM in the binder composition, but it did not comprise any AAEM in the additive.
  • Inventive Coating 8 and Comparative Coating 7 comprised equal amount of AAEM, the only difference was that AAEM was added in the binder in Comparative Coating 7, while added in the additive in Inventive Coating 8.
  • Inventive Coating 8 had a significantly better formaldehyde abatement effectiveness compared to that of Comparative Coating 7.
  • Comparative Coating 7 had the similar formaldehyde abatement effectiveness as Comparative Coating 9, and the AAEM loading in Comparative Coating 7 was 0.04%, while the AAEM loading in Comparative Coating 9 was only 0.02% by dry weight based on total dry weight of the coating composition.
  • AAEM loadings in the coating formulation limited coatings' formaldehyde abatement effectiveness, and would work only at a range of higher than 0.04% by dry weight based on total dry weight of the coating composition.
EP15898528.3A 2015-07-20 2015-07-20 A coating additive Active EP3325526B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/084426 WO2017011972A1 (en) 2015-07-20 2015-07-20 A coating additive

Publications (3)

Publication Number Publication Date
EP3325526A1 EP3325526A1 (en) 2018-05-30
EP3325526A4 EP3325526A4 (en) 2019-04-24
EP3325526B1 true EP3325526B1 (en) 2022-07-06

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EP15898528.3A Active EP3325526B1 (en) 2015-07-20 2015-07-20 A coating additive

Country Status (7)

Country Link
US (1) US10703918B2 (zh)
EP (1) EP3325526B1 (zh)
CN (1) CN107849186B (zh)
BR (1) BR112018000443A2 (zh)
CA (1) CA2992498C (zh)
MX (1) MX2018000740A (zh)
WO (1) WO2017011972A1 (zh)

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CN103555120B (zh) 2013-10-08 2016-06-01 雅图高新材料有限公司 一种聚丙烯酸酯接枝改性聚酯水性涂料及其制备方法
CN103965730B (zh) * 2014-05-22 2016-07-06 北京化工大学 一种超低voc释放水性涂料及其制备方法

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EP3325526A1 (en) 2018-05-30
EP3325526A4 (en) 2019-04-24
US20180194948A1 (en) 2018-07-12
MX2018000740A (es) 2018-05-15
CA2992498C (en) 2022-11-22
BR112018000443A2 (zh) 2018-09-11
CN107849186A (zh) 2018-03-27
CN107849186B (zh) 2021-03-16
WO2017011972A1 (en) 2017-01-26
US10703918B2 (en) 2020-07-07
CA2992498A1 (en) 2017-01-26

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